3, 4-methylenedioxyphenyl-propylene compound



Patented Dec. 21, 1948 UNITED STATES PATENT QFFICE 3,4-METHYLENEDIOXYPHENYL-PBOPYLENE COMPOUND Edward A. Prill, Yonkers, N. Y., asslgnor to Boyce Thompson Institute for Plant Research, Inc., a corporation of New York No Drawing.

4 Claims. 1

This invention relates to organic chemical compounds and has for its object the provision of certain new organic compounds and insecticidal compositions comprising the compounds. I have discovered a series of organic compounds which I have synthesized and found to be markedly active as insecticides. The compounds of the invention are effective insecticides alone and also increase the effectiveness of other insecticides.

' The .compounds of the invention compare favorably with or exceed the extracts of pyrethrin and rotenone bearing plants in toxicity to insects. In

where R is hydrogen, methyl or ethyl, and R1 and R2 may each be a member of the group consisting of an alkyl radical, an alkenyl radical, a cycloalkyl radical and an aralykyl radical, also, R1 may be hydrogen, also R1 andR: together may be a single divalent aliphatic hydrocarbon radical, such as in the type of amides known as piperidides, or a single similar divalent aliphatic radical which is interrupted by ethereal oxygen, such as in the type of amides known as morpholides.

The acids, of which the nitrogen substituted amides are insecticidal compounds, may be made by the peroxide catalyzed addition reaction of an Application January 16, 1946, Serial No. 641,631

aliphatic a-mercapto carboxylic acid, of the formula where R is as above, and a 3, 4-methylenedioxyphenyl-propylene, such as safrole or isosafrole. The acids subsequently may be reacted with an amine of the formula B an:

where R1 and R: are as above to produce the compounds. The compounds also may be made by the peroxide catalyzed addition reaction of an aliphatic c-mercapto nitrogen substituted amide of the formula R 0 R1 natal-M where R, R1 and R2 are as above, and a 3, 4- methylenedioxyphenyl-propylene, such as sairole or isosafrole.

The process used in making the compounds illustrating this invention is given below.

To a mixture consisting of 81 g. of safrole and 46 g. of mercaptoacetic acid, there was added a few drops of ascaridole, which is an organic peroxidic catalyst. The mixture was held at about C. for 48 hours for the reaction to take place. The crude product was then neutralized "with aqueous sodium hydroxide and any water- '3 and its melting point is 71 0. Its neutral equivalent was found to be 252.5, which agrees closely with the theoretical value of 254.3.

A mixture consisting of 81 g. of isosafrole and 46 g. mercaptoacetic acid with a few drops of added ascaridole was subjected to the same treatment as was used in the preceding synthesis. The yield of the new compound, which is a viscous oily liquid, was 95 g. This new compound, hereinafter referred to as acid II, has the probable formula: 1

and its distillation range is 208 to 212 C. at 2 mm. of mercury pressure. Its neutral equivalent was found to be 260, which agrees closely with the theoretical value of 254.3.

Acids I and II were converted into the various nitrogen substituted amides by making the intermediary acid chlorides and reacting a portion of each of the acid chlorides with an excess of one of several amines. This is a standard well known method of converting carboxylic acids to nitrogen substituted amides. In practice, any other suitable method can be used. The melting points of those amides which are solids are given with the data in Tables I and II. The other amides were very viscous oily liquids. The liquid amides of this invention, with the exception of the morpholldes, were soluble in Deo-Base, a .purifled petroleum distillate, the N,N-dibutylamides and the N,N-diamylamides being very soluble in this solvent. Solubility in such petroleum distillates' is a very desirable property of insecticidal compounds.

Similar compounds may be made by'starting with a-mercaptopropionic acid or a-mercaptobutyric acid in place of mercaptoacetlc acid.

Spray solutions containing the compounds 11- I lustrating this invention were tested against houseflies by the large group Peat-Grady method as outlined in Blue Book, page 1'77 (MacNair- Dorland Co., New York, 1939). Control tests with the Oflicial Test Insecticide (OTI), which contains approximately 0.1 g. pyrethrins per 100 ml. (Soap and Sanitary Chemicals 21 (6): 137 -141, June, 1945) were also performed with each batch of flies used. The solid amides and the morpholides were dissolved in a mixed solvent consisting of Dec-Base and not more than 10 per cent acetone, and the other liquid amides were dissolved in Dec-Base alone. Some of the compounds were tested without admixed pyrethrins. One or more solutions of each compound with admixed pyrethrins was tested. The amount of admixed pyrethrins was usually 0.025 g. per 100 ml. and this amount of pyrethrins alone gave, on testing, a 10 minute knockdown of only 84 per cent and a 24 hour kill of only 21 per cent when the 24 hour kill of the O'I'I was per cent.

The results of the tests on the amides derived from acid I- are given in Table I and the results of the tests on the amides derived from acid H are given in Table II. The compounds even without admixed pyrethrins show considerable paralyzing and killing ability. For fiy sprays it is more practical to use the compounds in admixtur with a minimum amount of pyrethrins, with which they exhibit synergistic action both in respect to the kill and in respect to the knockdown. Synergism in respect to kill is obvious from the data given for several of the compounds. Definite examples of synergism in regard to knockdown is provided by the data given for compounds 5 and 10. Thus a spray solution containing in admixture 0.1 g. of compound 5 and 0.0125 g. pyrethrins per 100 ml. gave a very sat isfactory knockdown of 99 per cent, while neither twice this concentration, namely, 0.2 g. of the compound per 100 ml. alone, nor twice this concentration, namely, 0.025 g. of pyrethrins per 100 ml., alone, ever gave a knockdown of over per cent. A similar situation is true in regard to the data for compound 10.

A very useful application of the ability of these compounds to greatly improve the knockdown when in admixture with 2,2-bis-p-chlorophenyl- 1,1,1-trichloroethane (DDT) and a minimum amount of pyrethrins is illustrated herein. DDT

is an excellent insect killer but it gives a very slow knockdown and pyrethrins are commonly admixed with it to impart rapid knockdown ability to the mixture. It is shown in the data for compounds 5 and 10 in Table I, that by halving that amount of the expensive pyrethrins, which in admixture with DDT gives an inadequate 10 minute knockdown, and adding a small amount of a compound of this invention, a satisfactory 10 minute knockdown and also a higher kill is obtained.

Some of the compounds which were tested against houseflies were also tested against certain agricultural insects. For these tests a weighed amount of a compound dissolved in 10 ml. of acetone was mixed with 90 ml. of a 0.1 per cent aqueous solution of sodium lauryl sulfate and the resulting emulsion sprayed upon insect infested leaves. After holding the sprayed insect infested leaves in Petri dishes'for 20 hours the results were determined.

When thus tested against Aphis rumicz's on nasturtium leaves, kills of 99 per cent were obtained with 0.1 per cent emulsions of compounds 5 and 13.

When thus tested against pea aphids on bush bean leaves, a kill of 100 per cent was obtained witha 0.1 per cent emulsion of compound 5.

When thus tested against a thrips species on chicory leaves, a kill of 100 per cent was obtained with a 0.1 per cent emulsion of compound 5.

When thus tested against red spider mites on bush bean leaves, a kill of 49 per cent was obtained with a 0.1 per cent emulsion of compound 13.

When similar tests were performed on Mexican bean beetle larvae on bush bean leaves with 0.2

per cent emulsions of compounds 10 and 21, a few of the larvae were killed, but it was significant that no feeding occurred within the 48 hour test period. Thus it is apparent that the compounds exhibit a repellant action against this insect.

In none of the above tests on agricultural insects did .the control spray, which contained only water, acetone,'and the emulsifying agent, give a kill of over 8 per cent.

It is to be understood that the compounds of Tables I and II are used merely as examples and the invention is not limited to these particular compounds. Also, the invention is not to be construed as limited to compounds made by means of that particular chemical reaction which was used for the making of the illustrative compounds. Also, the above examples are not to be construed as limiting either the method of application of these novel insecticides or the kinds 7 of insects to which they may be applied,

Increase Com- Compound which is de- Melting 24 Hr. pound rived from Acid I, and P olnt, 5 335" mu, 3" No. which is the- 0. pet cent per cent per cent 1 N-Ethylamide 61 4 95 58 51 +7 2 N w 50 4 72 e1 64 +3 2 96 55 50 3 N-lao-Butylamlda 41 .4 so as 40 +16 2 98 77 54 +23 4 N -A11ylamld0 74 4 97 53 5 +2 5 N-Oyclohoxylamlda.---. 85 4 92 52 89 +13 4 99 94 39 55 1 U 63 44 19 .05 9! 51 53 2 w. l 99 45 46 1 0 86 74 46 +28 6 N-Benzylamide 82 06 43 5 7 N,N-Dl-ethylalnid6 95 75 50 8 N ,N-Dl-n-propylamide.. 99 71 43 +28 9 N,N-D1-iso-pr,1 yla- 99 66 43 +23 mide.

10 N N-Di-n-Bu lamidm- 76 57 51 ty m 92 51 43? H 81 51 96 B5 49 16 99 45 +5 99 46 --I. 86 74 46 +28 N,N-Dl-amylam1de 1 96 a0 43 +11 N,N-Dlcyclohexy1am1de- 4 98 72 58 +14 Piperldide 8 87 80 53 27 .4 a1 59 +9 .2 100 as 7 52 +33 14 Morpholide 2 93 53 50 1 The lominutaknockdow'notthe OTIwaswithinthamnge ot95to 100 per cent inall cases.

10 min. Increase Com- 00111 11116 which is de- Melting 24 Hr. pound rive zl from Acid 11, and Point, 5:32 K 8119; 2 No. which is the- 0. per i per cent per cent- 15 N -n-Butylamide 62 99 86 +29 N-iso-Butylamlde 74 2 96 73 +16 16 N-Gyc1ohexy1amide 100 4 88 38 -1 .4 99 94 .2 99 83 +44 1 99 +27 05 97 51 2 17 N-Benzylamide 4 76 23 12 2 96 65 +30 18 N,N-Di-ethylamide 2 59 51 +8 19 N ,N-Di-n-propylamide 2 97 79 57 +22 20 N,N-Dl-iso-propylamide 2 93 70 55 +15 21. N,N-Di-n-buty1am1de 4 65 40 55 15 2 97 65 55 +10 22 N,N Di-amylamide .2 91 64 55 +9 23 Piperidide .s as 81 53 +34 2 99 87 52 +35 24 Morpholide 96 51 52 1 1 The 10 minute knockdown of the 0'1I was within the range of 95 to per cent in all cases.

7 8 I claim: 4. A compound having the formula: 1. A compound represented by the formula: o

R o o oirm-s-omi-mnm o (umo-s-dn-t'a-z/ 6 H10 H'\ Bs \o EDWARD A. PRILL. where R, is a member of the group consisting of hydrogen, methyl, and ethyl; R1 and R2 10 REFERENCES CITED taken together comprise at least one member The following references are of record in the of the group consisting of hydrogen, alkyl, file Of this Patent:

,alkenyl, cycloalkyl, divalent polymethylene and UNITED STATES PATENTS divalent polymethylene interrupted by ethereal Number Name Date oxygen; not more than one of the R1 and R2 15 2 350 G m t 1 10, 19 3 groups being hy r n. 2,362,128 Gertler et a1. Nov. 7, 1944 h in i rmul 2 A av g the OTHER REFERENCES Soap and Sanitary Chemicals, June 1943, by Roarck, pages 95 and 96.

H Hm l Contributions Boyce Thompson Institute, Jan. 1946, volume 14, pages 127-150, by Prill et a1. 3. A compound having the formula:

- O 01H: o cim)-s-om- -n 25 Bio C|Hl 

